Process for producing fast dyeings on the fiber



PM Aug. 14, 1928.

UNITED STATES r e: mar-mm, amour, assronoas, BY

- nrns'rurr conronarron, or new roux, n. 1., a consonaa'ron on PATENT OFFICE.

,0I'DESSAUIIANHAL'LAHDIO em or assrc no FOR PRODUCING FAST DYEHI'GS ON THE mm In Drawing. Application fled January 21, 1927, Serial In 182,678, and in Germany January 88, III.

A known method of producing fast dyeings on the fiber consists in im regnatmg the fiber with a compound adapte to be coupled and then treating the fiber with a solutlon I of a diazo compound. In cases in which the compound ada to be coupled has a certain afiinity or the fiber it IS sufiicient merely to'wring out the impregnated fiber and to conduct the coupling without previously drym' In producing printed colors, the materia is previously prepared with a compound ada ted to be coupled, such as for example droxynaphthalene, and is printed with a thickened diam-solution; or the material may be printed with a mlxture of an alkali compound of a 2-hydroxynaphthalene carboxylic acid arylamide an a dzable diazo com ound, after which the material is steam or exposed to the air and the dyeing developed by treatment with an acid.

In the hows process difliculties are associated with the diazotization. By the present invention these difiiculties are avoided and the process is conducted very simply by carrying out the preparation of e diazo compound on the fiber where t unites directly with the coupling component. The preliminary pre aration of a dimsolution or the use a stable diazo compound is accordingly unnecessary.

In the copending a plication Serial Number 62,149 filed Octo r 12, 1925, there are described preferred 'procedures for the pre aration of diazo compound on the fiber and its combination with coupling component present on the fiber. We do not claim what is disclosed and claimed in the mentioned application but only an improvement of said mvention.

According to the present improvement the invention may be carried out as follows:

The fibrous material, such as artificial silk consisting of cellulose acetate, pelts, hairs, feathers, after ha been impregnated with a mixture containing a diazotizable compound, a compound adapted to coupled and a nitrite is treated with an'ac1d medium, preferably in the same bath by adding an acid agent to the bath.

If in the dyeing of pelts, hairs, feathers or the like two baths are used, the goods to be dyed, which have been saturated with the said mixture, are wrung out or centr' d and then brought into an acid bath, to which some nitrite may advantageously be added.

To the dye bath may be added materials necessary for the so-called killing process in order to decrease and purify the pelts, hairs or the like which are to be dyed and to make them receptive of the dye. Also materials' which protect fibers may be added to the bath.

The invention may also be carried out by treating the fiber with a mixture of a compound adapbed to be coupled and a nitrite and then, after drying, with a solution containing a salt of a diazotizable base, preferably with an addition of an organic acid. One of the treatments with chemicals may be executed b printing.

If the fiber 1s impregnated with a mixture containing a diazotizable compound, a compound adapted to be coupled and a nitrite, fast dyeings may be produced by printing on an acid medium, for instance a mixture containin an organic acid.

The f0 owing examples, without limiting the invention, serve to illustrate in which manner the process may be carried out:

Example 1.20 grams of cellulose acetate silk are handled for about 30 minutes at (Hi-70 C. in 500 cc. of a liquor containing per liter 0.4 gram of aminoazobenzene, 5

cc. of a solution of the sodium 2-hydroxynaphthalene (1:10), 50 cc. of Monopol soap solution (1 and 50 cc. of sodium nitrite solution (1:10). 7 There are then added to the liquor cc. of acetic acid of 6 B6. and the acetate silk is handled for further 20-30 minutes atthe said temperature. There is thus obtained a bright red dyein 3 Example 2.20 grams of cell ose acetate silk are handled for about minutes at 6070 C. .in 500 cc. of a, liquor which contains per liter 0.3 gram of dichlorobenzidine, 10 cc. of sodium 2-hydroxynaphthalene solution (1:10), 10 cc. Turkey red oil of per cent strength and 50 cc. of sodium nitrite solution (1: 10). The development of the dyeing is conducted as described in Example 1. There is obtained a bright orange dyeing.

Example 52-20 ams of cellulose acetate silk are handled or about minutes at 6070 C. in 500 cc. of a liquor which contains per liter 0.1 gram of dianisidine, 1.2 gram of sodium 2-hydroxynaphthalene-3- carboxylate, 6 cc. of Turkey red oil of per cent strength and 25 cc. of sodium n1- trite solution 1:10). After development in the manner escribed in Example 1 there is obtained a medium blue.

Eaample 4.20 grams of cellulose acetate silk are handled for about 30 minutes at 70 C. in 500 cc. of a liquor containing per liter 0.8 gram of dianisldine, 1.5 gram of sodium 2-hydroxynaphthalene-? -carboxylate, 50 cc. of Monopol-soap solution (1 :20) and 50 cc. of sodium nitrite solution (1: 10). After development in the manner described in Example 1 there is obtained a black dyem 'n iaample 5.-In 'a bath containing per liter 2 grams of I 5-nitro-2.4-diam1no-1- methylbenzene, 25 cc. of Monopol soa solution (1 :20), 10 cc. of a solution of so mm 2-hydroxynaphthalene (1:10) and 100 cc. of sodium nitrite solution (1:10), a well killed skin is handled for 2 hours at the ordinary temperature. After addition of 50 cc. of acetic acid of 6 B. the skin is further handled for about 30 minutes. There is obtained a brownish yellow dyeing.

Example 6.-In a bath containin per liter 3 grams of -5-nitro-2.4-diammo-1- methylbenzene, 25 cc. of Monopol soap solution (1 :20), 4 grams of sodium 2-hydroxyna hthalene-3-carboxylate and 100 cc. of so ium nitrite solution (1:10), a skin is handled for about 30 minutes at the ordinary temperature. The further treatment is conducted as described in Example 5. There is obtained a co per red dyeing.

Example ?'.-In a ath containing per liter 5 grams of 2-hydroxynaphthalene-3- carboxylic acid 2methyl-4-chlorophenylamide, 10 cc. of Turkey red oil, 7 cc. of sodium hydroxide solution of 34 B., 5 cc.

of formaldehyde of .30 per cent strenlgl'th,

3.6 grams of 6-chloro-2-amino-1-met ylbenzene, 100 cc. of sodium nitrite solution (1 :10) and a fiber protecting agent, for example 5 cc. of Protectol Agfa, a skin is handled for 2 hours. The further treatment is conducted as described in Example 5. There is obtained a scarlet dyeing.

Eaample 8.-In a bath containing per liter 6 grams of 5-nitro-2.4-diamino-1- methylbenzene, 1.8 am of l-amino-na hthaleue, 50 cc. of onopol soap solutlon (1:20), 10 cc. of sodium 2-hydroxynaphthalene solution (1:20) and 300 cc. of sodium nitrite solution (1 10) a skin is handled for 2 hours. The further treatment is con-" ducted as described in Example 5. There is obtained a dark brown dyeing.

Example 9.In a bath containing per liter 0.6 gram of l-aminonaphthalene, 25 cc. of Monopol soap solution (1:20), 1 gram of sodium 2-hydrox naphthalene-il-carboxylate and 150 cc. 0 sodium nitritesolution 1: 10) a skin is handled for 2 hours. After urther treatment as described in Example 5, there is obtained an olive green dyeing.

Example 10.-In a bath containing per liter 3.6 grams of l-aminonaphthalene, 50 cc. of Monopol soap solution (1:20), 5.2 grams of sodium 2-hydroxynaphthalene-3- carboxylate and 300 cc. of sodium nitrite solutlon (1:10 a skin is handled for about 2 hours. A r further treatment as described in Example 5 a black dyeing is obtained.

Eaample 11.-A skin is handled for about 2 hours in a bath containing per liter 4 ams of l-aminonaphthalene, 50 cc. of

onopol soap solution (1:20), 5.2 grams of sodium 2-hydrox na hthalene-3-carboxylate and 300 cc. 0 so ium nitrite solution SFIO). The skin is then wrung out and t e dye is develo ed by introducing the skin into a fresh bat containing per liter 100 cc. of sodium nitrite solution (1:10) and 50 cc. of acetic acid of 6 B. There is obtained a black dyeing.

After dyeing the skin is well washed, which is also 'done in the other cases. For enhancing the -fastness to rubbing the skin may be finally soaped.

E mample 12.The skin is handled at ordinary temperature for about 2 hours in a bath containing per liter 3.6 grams of l-aminonaphthalene, 50 cc. of Monopol soap solution (1:20), 5.2 grams of sodium 2-hydroxynaphthalene-3-carboxylate, 100 cc. sodium nitrite solution (1:10), 5 cc. ammonia of 25 per cent strength and 30 grams of sodium chloride and the handling is continued for about 30 minutes after addition of 10 cc. formic acid of 85 per cent strength to the bath. When the dyeing is complete the skin is well washed. ere is obtained a black d eing.

Ewamp 13.3 grams 'of di-acetoacetic acid-ortho-tolidinide, 3 cc. of Turkey red oil, 4.5 cc. of sodium hydroxide solution of 34 B6. and 2 grams of sodium nitrite are dissolved in 40 cc. of water. After addition of 40 grams of neutral starch-tragacanth thickening (6:100) the mixture is printed on unprepared goods. After drying there follows at the ordinary temperature a treatment with a solution of 5 ams of 2-chloro-1- aminobenzene hydroch oride and 20 grams of aluminium sulfate per liter. The goods are washed and soaped hot. There is obtained a clear yellow.

Example 14.There are mixed together solutions of 5 grams of the sodium salt of the acid sulfuric acid ester of leuco-indigo in 20 cc. ofwater and 5 grams of di-acetoacetic acid-ortho-tolidinide, 5 cc. of Turkey Ian 1,eae,ro1 3 red oil, 7.5 cc. of sodium hydroxide solution and 20 grams of sodiumnitrite They are of 34 B. in 20 cc. of water and 4 grams of then dried and printed with a mixture of 16 sodium nitrite in cc. of water; to these grams 2-chloro-1-a1ninobenz .ene hydrochlosolutions 50 grams of neutral starch-tragaride, 50 grams of glycolic acid, 434 grams of canth thickening (6: 100) are admixed. water and 500 grams of neutral starch-trag- 7" The unprepared goods are printed with the acanth thickening. They are then washed, mixture, dried and then treated with a boilsoaped, further washed and dried. There ing hot solution containing per liter 0.95 is obtained a clear greenish yellow dyeing. gram of 2.5-dichloro-1-aminobenzenehydro- Example 19.The goods are saturated chloride, 3 0c. of hydrochloric acid of with a solution containing per liter grams 7 136., grams of sodium chloride and 12.5 of 2-hydroxynaphthalene, made into a paste grams of aluminium sulfate. After they with 25 grams of sodium hydroxide solution are washed the goods are soaped hot. There of 34 Be. and 20 grams of Turkey red oil is obtained a green d elng. (sodium salt) and dissolved in water, and

Exam 15.1.25 gram 2-hydroxynaph- 30 grams of sodium nitrite. After the goods thalene- -carboxylic acid phenylamide, 3 have been dried they are printed with a mixcc. of Turkey red oil, 2.2 cc. of sodium ture of 30 grams of l-aminonaphthalene hydroxide solution of 34 B. and 3.8 grams hydrochloride, 30 grams of formic acid of of sodium-nitrite are dissolved in 40 cc. of per cent strength, 440 grams of water water. After addition of 40 grams of neuand 500 grams of neutral starch-tragacanth 35 tral starch-tra acanth thickening (6; thickening, and are then washed and soaped. the unprepared goods are rinted with the There is obtained a deep Bordeaux tint. mixture. They are then ried and intro Ewample 20.-The goods are saturated duced into a boiling hot solution containing with a. solution containing per liter 20 grams gr liter 0.95 gram of 2.5-dichloro-1-aminoof 2-hydroxynaphthalene-3-carhoxylic acid nzene hydrochloride and 15 grams of phenylamide, 30 cc. of sodium hydroxide aluminium sulfate. They are then washed solution of 34 136., 20 cc. of Turke red oil and hot soaped. There is obtained a red- (sodium salt) and 30 grams of so ium nidish orange dyeing. trite. After they have been dried the goods Example 16'.-1 gram of 2-hydroxynapb are printed with a mixture of 24 grams of 2- thalene-S-carboxylic acid--methoxyphenylamino-1 -methoxybenzene-azo-l-aminonaphamide, 3 cc. of sodium hydroxide solution of thalene (or the corresponding sulfamino 34 B6. 1.5 cc. of Turke red oil and 2 grams acid), 8 grams of hydrochloric acid of 20 of sodium nitrite are 'ssolved in 40 cc. of B6. 40 grams of acetine, 24 grams of formic water. After addition of 40 grams of neuacid of 90 per cent grams of tral starch-tragacanth thickening (6:100) lactic acid of 100. er cent strength, 324 the unprepared goods are prints with this grams of water and 500 grams of neutral mixture. After the have been dried they starch tragacanth thickening. They are are treated with a oiling hot solution of then dried, washed and soaped hot. There 0.5 gram. l-methyl-2-amino-5-nitrobenzene, is obtained a neutral black. 7.5 cc. of acetic acid of 30 per cent strength, Example 21.The goods are impregnated 50 grams of sodium chloride and 5 grams with a solution con ining er liter 30 aluminium sulfate per liter. After they have grams of 2.4-diamino-1-methylbenzene, 20 been rinsed they are soaped hot. There is grams of Turkey red oil and 30 grams of obtained a Bordeaux tint sodium nitrite. They are then printed with Example 17.'H1e goods are saturated a mixture consisting of 50 grams of oxalic with a solution containing per liter 5 grams acid, 450 grams of water and 500 grams of of 2-hydroxynaphthalene-i-carboxylic acidstarch-tragacanth thickening. They are 3-nitrophenylamide, 7.5 cc. of sodium hythen washed and soaped as usual. The droxide solution of 34 B., 10 cc. of Turkey shade obtained is a dull brown. red oil (sodium salt) and 10 grams of What we claim is: sodium nitrite. After dryi the goods are 1. A recess for producing fast dyeings printed with the mixture of 5 ams l-methon the dber which consists in diazotizing a oxy-2-amino-5-nitrobenzene ydrochloride, diazotizable amine on the fiber in presence 50 grams of lactic acid of 50 per cent of a compound to be con led. strength, 445 grams of water and 500 grams 2'. A process for pro ucing fast dyeiltilgs e of neutral starch-tragacanth thickening. on the fiber which consists in treating They are then dried, washed, soaged hot, fiber first with a mixture cont a dimwashed, first hot and then cold, an finally otizable compound, a compound adapted to dried. There is obtained a bluish rose color. be coupled and a nitrite, and then with an Ewample 18.-The goods are saturated acid medium.

with a solution containing per liter 20 grams 3. A rooess for producing fast dyeings of di-acetoacetic acid-ortho-tolidinide, 30 on the her which consists in reating the cc. of sodium hydroxide solution of 34 B., fiber first with a mixture containing a di- 5 20 grams of Turkey red oil (sodium salt) azotizable compound, a compound adapted ill fiber first with a. mixture containing a diazotizable compound, a compound adapted to be coupled and a. nitrite, and then printing on an acid medium.

6. A rocess for producing fast dyeings on the Eber which consists in treating the fiber first with a mixture containing a diazotizable compound, a compound adapted to be coupled and a nitrite, and then printing on an acid medium containing an organic acid.

In testimony whereof we have aflixed our signatures.

THEODOR KIRCHEISEN.

J OHAN NES GU'RTLER.

. CERTIFICATE OF CORRECTION.

Patent No. l, 680, 791.

Granted August 14, 1928, to

THEODOR KIRCHEI SEN, ET AL.

1 It is hereby certif ied'that error appears in th above numbered patent requiring correction as fol] I "degrcase": and that th with tlus correction therein that the same 111 word "decrease" read in the Patent Office.

Signed and sealed this 2nd day of October, A. '0. 192a.

M. J. Moore,-

Acting Commissioner of Patents.

e printed specification of the ows: Page 1, line 59, for the c said Letters Patent should be read ay conform to the record of the case ill fiber first with a. mixture containing a diazotizable compound, a compound adapted to be coupled and a. nitrite, and then printing on an acid medium.

6. A rocess for producing fast dyeings on the Eber which consists in treating the fiber first with a mixture containing a diazotizable compound, a compound adapted to be coupled and a nitrite, and then printing on an acid medium containing an organic acid.

In testimony whereof we have aflixed our signatures.

THEODOR KIRCHEISEN.

J OHAN NES GU'RTLER.

. CERTIFICATE OF CORRECTION.

Patent No. l, 680, 791.

Granted August 14, 1928, to

THEODOR KIRCHEI SEN, ET AL.

1 It is hereby certif ied'that error appears in th above numbered patent requiring correction as fol] I "degrcase": and that th with tlus correction therein that the same 111 word "decrease" read in the Patent Office.

Signed and sealed this 2nd day of October, A. '0. 192a.

M. J. Moore,-

Acting Commissioner of Patents.

e printed specification of the ows: Page 1, line 59, for the c said Letters Patent should be read ay conform to the record of the case 

